Mould-resistant emulsion paints

ABSTRACT

The application relates to emulsion paints which are protected against fungal infestation by the use of N-alkyl-benzothiophene-2-carboxamide S,S-dioxides.

The invention relates to mould-resistant emulsion paints which contain as fungicide N-alkyl- preferably N-cyclohexyl-benzothiophene-2-carboxamide S,S-dioxide and which remain free from fungus and stable in colour permanently, i.e. even after exposure in warm ambient air and humidity (condensation or rain) or after thermal stress.

Benzothiophene-2-carboxamide S,S-dioxides (BCD's), a process for their preparation and their fungicidal action are known (DE-A-41 15 184). A description is given in particular of their activity against phytopathogenic fungi and dematophytes. It is also stated that BCD's are suitable for the protection of industrial materials against microbial alteration or destruction. Among the industrial materials mentioned are coating compositions. The majority of the BCD's described, however, when in alkaline media, for example in emulsion paints, undergo hydrolysis to liberate aniline derivatives, which are known to have a strong tendency towards autoxidation, a process in which they become discoloured, so that these BCD's cannot be considered for use as paint fungicides in emulsion paints.

Suprisingly it has now been found that there are substances among the BCD's whose spectrum of action is so wide that it covers not only phytopathogenic fungi and dermatophytes but also the mould fungi which commonly grow on coatings. These compounds are, surprisingly, also so stable to hydrolysis and stable in colour that they are outstandingly suited to the production of mould-resistant emulsion paints. The application therefore relates to emulsion paints comprising N-alkyl-benzothiophene-2-carboxamide S,S-dioxides. Preferred N-alkyl compounds are those in which alkyl represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, n- or i-heptyl, n- or i-octyl, n- or i-nonyl, n- or i-decyl, n- or i-dodecyl, n- or i-octadecyl, or represents allyl, n- or i-nonyl, n- or i-decyl, n- or i-dodecyl, n- or i-octadecyl, or represents allyl, n- or i-butenyl, n- or i-pentenyl, n- or i-hexenyl, propargyl, n- or i-butinyl, n- or i-pentinyl, n- or i-hexinyl, chloromethyl, bromomethyl, chloroethyl, bromoethyl, chloropropyl, bromopropyl, cyanomethyl, cyanoethyl, cyanopropyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, methoxycarbonylmethyl, methoxycarbonylethyl, methoxycarbonylpropyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, ethoxycarbonylpropyl, propoxycarbonylmethyl, propoxycarbonylethyl, propoxycarbonylpropyl; and additionally represents cyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl or cyclohexylpropyl, each of which is optionally substituted from one to four times in the cycloalkyl moiety by identical or different substituents consisting of fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, chloromethyl, dichloromethyl or trifluoromethyl.

Particular preference is given to N-n-butyl-, N-n-pentyl-, N-n-hexyl-, N-cyclo-hexylmethyl-, N-cyclohexyl-benzothiophene-2-carboxamide S,S-dioxides.

Very particular preference is given to N-cyclohexyl-benzothiophene-2-carboxamide S,S-dioxide.

These compounds are distinguished by high thermal stability so that, unlike the other BCD's and other common commercial fungicides, they can be used without a loss in action in emulsion paints including those which are used for coating heat insulation panels, the coated panels being passed through a drying tunnel and exposed to relatively high temperatures.

The emulsion paints contain the paint fungicides which can be used in accordance with the invention, in this context, in quantities of 0.05-5%, preferably of 0.2-2%, based on film weight.

The paint fungicides which can be used in accordance with the invention are employed in emulsion paints both alone and together with other active ingredients, for example together with preservatives in order to ensure the stability of the emulsion paints on storage, but also together with other fungicides and/or algicides, insecticides, molluscicides.

By means of these combinations of active ingredients, the spectrum of action of the N-alkyl-benzothiophene-2-carboxamide S,S-dioxides is enlarged still further, or particular effects are achieved. In many cases, synergistic effects are obtained. If the combinations of active ingredient are present in specific weight ratios, the synergistic effect is evident with particular clarity. However, the weight ratios of the active ingredients in the combinations of active ingredients can be varied within a relatively large range.

In this context, preferred co-components are:

Triazoles:

amitrole, azocyclotin, BAS 480F, bitertanol, difenoconazole, fenbuconazole, fenchlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol, imibenconazole, isozofos, myclobutanil, metconazole, epoxyconazole, paclobutrazol, penconazole, propioconazole, (±)-cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, triticonazole, uniconazole and the metal salts and acid adducts thereof.

Imidazoles:

imazalil, pefurazoate, prochloraz, triflumizole, 2-(1-tert-butyl)-l-(2-chlorophenyl)-3-(1,2,4-triazol-l-yl)-propan-2-ol, thiazole carboxanilides such as 2',6'-dibromo-2-methyl-4-trifluoromethoxy-4'-trifluoromethyl- 1,3-thiazole-5-carboxanilides and the metal salts and acid adducts thereof.

Methyl(E)-2-[2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl]3-methoxyacrylate, methyl(E)-2-[2-[6-(2-thioamidophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate,methyl(E)-2-[2-[6-(2-fluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate,methyl(E)-2-[2-[6-(2,6-difluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate,methyl(E)-2-[2-[3-(pyrimidin-2-yloxy)yloxy)phenoxy]phenyl]-3-methoxyacrylate, methyl(E)-2-[2-[3-(5-methylpyrimidin-2-yloxy)-phenoxy]phenyl]3-methoxyacrylate, methyl(E)-2-[2-[3-(phenyl-sulfonyloxy)phenoxy]phenyl]-3methoxyacrylate, methyl(E)-2-[2-[3-(4-nitrophenoxy)phenoxy]phenyl]-3-methoxy-acrylatemethyl(E)-2-[2-phenoxyphenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3,5-dimethylbenzoyl)pyrrol-1-yl]-3-methoxyacrylate, methyl(E)-2-[2-(3-methoxyphenoxy)phenyl ]-3-methoxyacrylate,methyl(E)-2-[2-(2-phenylethen-1-yl)-phenyl]3-methoxyacrylate, methyl(E-2-[2-(3,5-dichlorophenoxy)pyridin-3-yl]-3-methoxyacrylate, methyl(E)-2-(2-(3-(1,1,2,2-tetrafluoroethoxy)phenoxy)phenyl)-3-methoxyacrylate, methyl(E)-2-(2-[3-alphahydroxybenzyl)phenoxy]phenyl)-3-methoxyacrylate, methyl(E)-2-(2(4-phenoxypyridin-2-yloxy)phenyl)-3-methoxyacrylate, methyl(E)-2-[2-(3-n-propyloxyphenoxy)phenyl]3-methoxyacrylate, methyl (E-2-[2-(3-isopropyloxyphenoxy)phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[3-(2-fluorophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl(E)-2-[2-(3-ethoxyphenoxy)phenyl]-3-methoxyacrylate, methyl(E)-2-[2-(4-tert.-butylpyridin-2-yloxy)phenyl]-3methoxyacrylate, methyl(E)-2-[2-[3-(3-cyanophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl(E)-2-[2-(3-methylpyridin-2-yloxymethyl)phenyl]-3-methoxyacrylate, methyl(E)-2-[2-[6-(2-methylphenoxy)pyrimidin-4-yloxy]phenyl]-3methoxyacrylate, methyl(E)-2-[2-(5-bromopyridin-2-yloxymethyl) phenyl]-3-methoxyacrylate, methyl(E)-2-[2-(3-(3-iodopyridin-2-yloxy)phenoxy)phenyl]-3-methoxyacrylate, methyl(E)-2-[2[6-(2-chloropyridin-3-yloxy) pyrimidin-4-yloxy]phenyl]-3methoxyacrylate, (E),(E)methyl-2-[2-(5,6-dimethylpyrazin-2-ylmethyloximinomethyl)phenyl]-3-methoxyacrylate, (E)-methyl-2-{2-[6-(6-methylpyridin-2-yloxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate, E,(E) methyl-2-{2-(3methoxyphenyl)methyloximinomethyl]phenyl}-3-methoxyacrylate, (E)methyl-2-{2(6-(2-azidophenoxy)-pyrimidin-4-yloxy]phenyl}3-methoxyacrylate, (E),(E)methyl2-{2-[6-phenylpyrimidin-4-yl)-methyloximinomethyl]phenyl}-3-methoxyacrylate, (E),(E)-methyl-2-{2-[(4-chlorophenyl)-methyloximinomethyl]phenyl}-3-methoxyacrylate, (E)methyl-2-{2-[6-(2-n-propylphenoxy)-1,3,5-triazin-4-yloxy]phenyl }-3methoxyacrylate (E),(E)methyl-2-{2-[(3-nitrophenyl)methyloximinomethyl]-phenyl }-3-methoxyacrylate;

Succinate dehydrogenase inhibitors such as:

fenfuram, furcarbanil, cyclafluramid, furmecyclox, Seedvax, metsulfovax, pyrocarbolid, oxycarboxin, shirlan, mebenil (mepronil), benodanil, flutolanil (Moncut);

Naphthalene derivatives such as:

terbinafine, naftifine, butenafine, 3-chloro-7-(2-aza-2,7,7-trimethyl-oct-3-en-5-ine); sulphenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet; captan, captofol; benzimidazoles such as carbendazim, benomyl, furathiocarb, fuberidazole, thiophonate-methyl, thiabendazole or salts thereof;

Morpholine derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph; aldimorph, fenpropidin and salts thereof with arylsulfonic acids, for example p-toluenesulphonic acid and p-dodecylphenyl-sulphonic acid;

Dithiocarbamates, cufraneb, ferbam, mancopper, mancozeb, maneb, metam, metiram, thiram zeneb, ziram:

Benzothiazoles such as 2-mercaptobenzothiazole;

benzaxnides such as 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamides;

boron compounds such as boric acid, boric esters, borax; formaldehyde and formaldehyde-donor compounds such as benzyl alcohol mono- (poly)-hemiformal, oxazolidines, hexa-hydro-S-triazines, N-methylolchloroacetamide, paraformadehyde, nitropyrine, oxolinic acid, tecloftalam;

tris-N-(cyclohexyldiazeniumdioxy)-aluminium, N-(cyclo-hexyldiazeniumdioxy)-tributyltin and K salts, bis-N-(cyclohexyldiazeniumdioxy)-copper.

N-Methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octyl-isothiazolin-3-one, N-octyl-isothiazolin-3-one, 4,5-trimethylene-isothiazolinones, 4,5-benzisothiazolinones, N-methylolchloroacetamide;

Aldehydes such as cinnamaldehyde, formaldehyde, glutaraldehyde, β-bromocinnamaldehyde; thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate, etc.; quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethaylammonium chloride;

Iodine derivatives such as diiodomethyl p-tolyl sulphone, 3-iodo-2-propinyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diido-2-propenyl ethylcarbamate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diido-2-propenyl alcohol, 3-iodo-2-propinyl n-butylcarbamate, 3-iodo-2-propinyl n-hexylcarbamate, 3-iodo-2-propinyl cyclohexylcarbamate, 3-iodo-2-propinyl phenylcarbamate;

Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorphen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol and the alkali metal and alkaline earth metal salts thereof.

Microbicides having an activated halogen group, such as chloroacetamide, bronopol, bronidox, tectamers such as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane, β-bromo-β-nitrostyrene;

Pyridines such as 1-hydroxy-2-pyridinethione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulphonylpyridine, pyrimethanol, mepanipyrim, dipyrithion;

Metal soaps such as tin, copper and zinc naphtenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;

Metal salts such as copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate, copper sulphate, copper chloride, copper borate, zinc fiuorosilicate, copper fiuorosilicate.

Oxides such as tributyltin oxide, Cu₂ O, CuO, ZnO;

dialkyldithiocarbamates, such as Na salts and Zn salts of dialkyldithiocarbamates, tetramethylthiuram disulphide, potassium N-methyl-dithiocarbamate;

Nitrilessuchas2,4,5,6-tetrachloroisophthalodinitrile, disodium cyano-dithioimidocarbamate;

quinolines such as 8-hydroxyquinoline and the Cu salts thereof;

mucochloric acid, 5-hydroxy-2(5H)-furanone;

4,5-dichlorodithiazolinone, 4,5-benzodithiazolinone, 4,5-trimethylenedithiazolinone,

4,5-dichloro-(3H)-1,2-dithiol-3-one, 3,5-dimethyl-tetrahydro-1,3,5-thiadiazin-2-thione, N-(2-p-chlorobenzoylethyl)-hexaminium chloride, potassium N-hydroxym methyl -N'-methy 1-dithiocarbamate,

2-oxo-2-(4-hydroxy-phenyl)acethydroximic acid chloride,

phenyl (2-chloro-cyano-vinyl) sulphone,

phenyl 1,2-dichloro-2-cyano-vinyl sulphone;

Ag, Zn or Cu-containing zeolites alone or enclosed in polymeric active ingredients;

Very particularly preferred mixtures are those with azaconazole, bromuconazole, cyproconazole, dichlobutrazol, diniconazole, hexaconazole, metaconazole, penconazole, propiconazole, tebuconazole, methyl (E)methoximino[α-(o-tolyloxy)-o-tolyl)]acetate, methyl-(E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yl-oxy]phenyl}-3-methoxyacrylate, methfuroxam, carboxin, fenpiclonil, 4-(2,2-difluoro-1,3-benzodioxol-4-yl)-1H-pyrrole-3-carbonitrile, butenafine, imazalil, N-methyl-isothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, N-octylisothiazolin-3-one, benzisothiazolinones, N-(2-hydroxypropyl)-aminomethanol, benzyl alcohol (hemi)-formal, glutaraldehyde, omadine, dimethyl dicarbonate, and/or 3-iodo-2-propinyl n-butylcarbamate.

Furthermore, highly active mixtures are also prepared with the following active ingredients:

Fungicides:

acypetacs, 2-aminobutane, ampropylfos, anilazine, benalaxyl, bupirimate, quinomethionate, chloroneb, chlozolinate, cymoxanil, dazomet, diclomezine, dichloram, diethofencarb, dimethirimol, diocab, dithianon, dodine, drazoxolon, edifenphos, ethirimol, etridiazole, fenarimol, fenitropan, fentin acetate, fentin hydroxide, ferimzone, fluazinam, fluromide, flusulfamide, flutriafol, fosetyl, fthalide, furalaxyl, guazatine, hymexazol, iprobenfos, iprodione, isoprothiolane, metalaxyl, methasulfocarb, nitrothal-isopropyl, nuarimol, ofurace, oxadiyl, perflurazoate, pencycuron, phosdiphen, pimaricin, piperalin, procymidone, propamocarb, propineb, pyrazophos, pyrifenox, pyroquilone, quintozene, tar oils, tecnazene, thicyofen, thiophanate-methyl, tolclofos-methyl, triazoxide, trichlamide, tricyclazole, triforine, vinclozolin.

Insecticides:

phosphoric esters such as azinphos-ethyl, azinphos-methyl, α-1(4-chlorophenyl)-4-(O-ethyl, S-propyl)-phosphoryloxy-pyrazole, chlorpyrifos, coumaphos, demeton, demeton-S-methyl, diazinon, dichlorvos, dimethoate, ethoate, ethoprophos, etrimfos, fenitrothion, fenthion, heptenophas, parathion, parathion-methyl, phosalone, phoxim, pirimiphos-ethyl, pirimiphos-methyl, profenofos, prothiofos, sulfprofos, triazophos and trichlorphon;

Carbamates such as aldicarb, bendiocarb, α-2-(1-methylpropyl)-phenylmethylcarbamate, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb;

Organosilicon compounds, preferablydimethyl(phenyl)silyl-methyl 3-phenoxybenzyl ethers such as dimethyl-(4-ethoxyphenyl)-silylmethyl 3-phenoxybenzyl ether or (dimethylphenyl)-silyl-methyl-2-phenoxy-6-pyridyl methyl etherssuchas, for example, dimethyl-(9-ethoxy-phenyl)-silylmethyl-2-phenoxy-6-pyridyl methyl ether or [(phenyl)-3-(3-phenoxyphenyl)-propyl](dimethyl)-silanes such as, for example, (4-ethoxyphenyl)-[3-(4-fluoro-3-phenoxyphenyl-propyl]dimethyl-silane, silafluofen;

Pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin, cycloprothrin, cyfluthrin, decamethrin, cyhalothrin, cypermethrin, deltamethrin, alphacyano-3-phenyl-2-methylbenzyl 2,2-dimethyl-3-(2-chloro-2-trifluoro-methylvinyl)-cyclopropanecarboxylate fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin and tralomethrin;

Nitroimines and nitromethylenes such as 1-[(6-chloro-3-pyridinyl)-methyl]-4,5-dihydro-N-nitro-1H-imidazole-2-amine (imidacloprid), N-[(6-chloro-3-pyridyl)methyl-]N² -cyano-N¹ -methylacetamide (NI-25);

abamectin, AC 303, 630, acephate, acrinathrin, alanycarb, aldoxycarb, aldrin, amitraz, azamethiphos, Bacillus thuringiensis, phosmet, phosphamidon, phosphine, prallethrin, propaphos, propetamphos, prothoate, pyraclofos, pyrethrins, pyridaben, pyridafenthion, pyriproxyfen, quinalphos, RH-7988, rotenone, sodium fluoride, sodium hexafluorosilicate, sulfotep, sulfuryl fluoride, tar oils, teflubenzuron, tefluthrin, temephos, terbufos, tetrachlorvinphos, tetramethrin, 0-2-tert.-butyl-pyrimidin-5-yl-o-isopropyl-phosphorothiate, thiocyclam, thiofanox, thiometon, tralomethrin, triflumuron, trimethacarb, vamidothion, Verticillium Lacanii, XMC, xylylcarb, benfuracarb, bensultap, bifenthrin, bioallethrin, MERbioallethrin (S)cyclopentenyl isomer, bromophos, bromophos-ethyl, buprofezin, cadusafos, calcium polysulfide, carbophenothion, cartap, quinomethionate, chlordane, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpicrin, chlorpyrifos, cyanophos, beta-cyfluthrin, alpha-cypermethrin, cyophenothrin, cyromazine, dazomet, DDT, demeton-S-methylsulphon, diafenthiuron, dialifos, dicrotophos, diflubenzuron, dinoseb, deoxabenzofos, diazacarb, disulfoton, DNOC, empenthrin, endosulfan, EPN, esfenvalerate, ethiofencarb, ethion, etofenprox, fenobucarb, fenoxycarb, fensulfothion, fipronil, flucycloxuron, flufenprox, flufenoxuron, fonofos, formetanate, formothion, fosmethilan, furathiocar'b, heptachlor, hexaflumuron, hydramethylnon, hydrogen cyanide, hydroprene, IPSP, isazofos, isofenphos, isoprothiolane, isoxathion, iodfenphos, kadethrin, lindane, malathion, mecarbam, mephosfolan, mercurous, chloride, metam, Metarthizium, anisopliae, methacrifos, methamidophos, methidathion, methiocarb, methoprene, methoxychlor, methyl isothiocyanate, metholcarb, mevinphos, monocrotophos, naled, Neodiprion sertifer NPV, nicotine, omethoate, oxydemeton-methyl, pentachlorophenol, petroleum oils, phenothrin, phenthoate, phorate;

Molluscicides:

fentin acetate, metaldehyde, methiocarb. niclosamide, thiodicarb, trimethacarb;

Algicides:

copper sulphate, dichlororphen, endothal, fentin acetate, quinoclamine;

Herbicides:

    ______________________________________                                         acetochlor           benzofencap                                               acifluorfen          benzthiazuron                                             aclonifen            bifenox                                                   acrolein             bilanafos                                                 alachlor             borax                                                     alloxydim            bromacil                                                  ametryn              bromobutide                                               amidosulfuron        bromofenoxim                                              amitrole             bromoxynil                                                ammonium sulphate    butachlor                                                 anilofos             butamifos                                                 asulam               butenachlor                                               atrazine             butralin                                                  aziprotryne          butylate                                                  benazolin            carbetamide                                               benfluralin          CGA 184927                                                benfuresate          chloramben                                                bensulfuron          chlorbromuron                                             bensulide            chlorbufam                                                bentazone            chlorflurenol                                             chloridazon          difenoxuron                                               chlorimuron          difenzoquat                                               chlormethoxyfen      diflufenican                                              chlornitrofen        dimefuron                                                 chloroacetic acid    dimepiperate                                              achloropicrin        dimethachlor                                              chlorotoluron        dimethametryn                                             chloroxuron          dimethipin                                                chlorprepham         dimethylarsinic acid                                      chlorsulfuron        dinitramine                                               chlorthal            dinoseb acetate                                           chlorthiamid         dinoseb                                                   cinmethylin          dinoseb                                                   cinofulfuron         dinoseb acetate                                           clethodim            dinoterb                                                  clomazone            diphenamid                                                clomeprop            dipropetryn                                               clopyralide          diquat                                                    cyanamide            dithiopyr                                                 cyanazine            diuron                                                    cycloate             DNOC                                                      cycloxydim           PPX-A788                                                  2,4-D                DPX-E96361                                                daimuron             DSMA                                                      dalapon              eglinazine                                                dazomet              endothal                                                  2,4-DB               epsorcarb                                                 desmedipham          EPTC                                                      desmetryn            ethalfluralin                                             dicamba              ethidimuron                                               dichlobenil          ethofumesate                                              dichlorprop          fenoxaprop                                                dichlorprop-P        fenoxaprop-P                                              diclofop             fenuron                                                   diethatyl            flamprop                                                  flamprop-M           MCPA-thioethyl                                            flazasulfuron        MCPB                                                      fluazifop            mecoprop                                                  fluazifop-P          mecoprop-P                                                fluchloralin         mefenacet                                                 flumeturon           mefluidide                                                fluorocgycofen       metam                                                     fluoronitrofen       metamitron                                                flupropanate         metazachlor                                               flurenol             methabenzthiazuron                                        fluridone            methazole                                                 flurochloridone      methoprotryne                                             fluroxypyr           methyldymron                                              fomosafen            methylisothiocyanate                                      fosamine             metobromuron                                              furyloxyfen          metolachlor                                               glufosinate          metoxuron                                                 glyphosate           metribzin                                                 haloxyfop            metsulfuron                                               hexazinone           molinate                                                  imazamethabenz       monoalide                                                 imazapyr             monolinuron                                               imazaquin            MSMA                                                      imazethapyr          naproanilide                                              ioxynil              napropamide                                               isopropalin          naptalam                                                  isoproturon          neburon                                                   isouron              nicosulfuron                                              isoxaben             nipyraclofen                                              isoxapyrifop         norflurazon                                               lactofen             orbencarb                                                 lenacil              oryzalin                                                  linuron              oxadiazon                                                 LS830556             oxyfluorfen                                               MCPA                 paraquat                                                  pebulate             simetryn                                                  pendimethalin        SMY 1500                                                  pentachlorophenol    sodium chlorate                                           pentanochlor         sulfometuron                                              petroleum oils       tar oils                                                  phenmedipham         TCA                                                       picloram             tebutam                                                   piperophos           tebuthiuron                                               pretilachlor         terbacil                                                  primisulfuron        terbumeton                                                prodiamine           terbuthylazine                                            proglinazine         terbutryn                                                 prometon             thiazafluron                                              prometryn            thifensulfuron                                            propachlor           thiobencarb                                               propanil             thiocarbazil                                              propaquizafop        tioclorim                                                 propazine            tralkoxydim                                               propham              tri-allate                                                propyzamide          triasulfuron                                              prosulfocarb         tribenzuron                                               pyrazolynate         triclopyr                                                 pyrazosulfuron       tridiphane                                                pyrazoxyfen          trietazine                                                pyributicarb         trifluralin                                               pyridate             UBl-C4874                                                 quinclorac           vernolate                                                 quinmerac                                                                      quinoclamine                                                                   quizalofop                                                                     quzlzalofop-P                                                                  S-23121                                                                        sethoxydim                                                                     sifuron                                                                        simazine                                                                       ______________________________________                                    

The weight ratios of the active ingredients in these combinations of active ingredients can be varied within relatively large ranges.

The combinations of active ingredients preferably obtain the active ingredient in an amount of from 0.1 to 99.9%, in particular from 1 to 75%, particularly preferably from 5 to 50%, the remainder up to 100% being made up by one or more of the abovementioned co-components.

The term emulsion paints refers to aqueous coating compositions which have been rendered alkaline and are based on polymer dispersions which act as binder. Polymer dispersions which are frequently used to produce emulsion paints contain, for example, polyacrylates, styrene acrylates, polyvinyl acetate, polyvinyl propionate and other polymers. The attached formulations A, B and C give information by way of example on the composition of emulsion paints.

Coats of emulsion paints become infested by fungus in a humid environment, for example in the tropics, but also in humid rooms, in the foodstuffs or textile industry, in bathing halls, saunas and similar facilities, within a few months; in other words, a large number of different types of fungus propagate on the coatings. Fungal infestation of the coatings can also be permanently prevented, however, by incorporating a suitable fungicide into the coating compositions, for example by dispersing it with the pigments. With regard to such paint fungicides for emulsion paints, the person skilled in the art places the following requirements on them:

broad spectrum of action

virtually insoluble in water

not volatile

not discolouring

not odour-polluting

low toxicity/ecotoxicity

The substances according to the invention meet these requirements to a high level. Thus for the first time paint fungicides are available which can be employed effectively and without problems in emulsion paints.

The examples which follow serve to illustrate the invention. The invention is not, however, limited to the examples.

For testing the mould resistance of emulsion paints, the following procedure is adopted:

The coating composition to be tested is painted onto both sides of a suitable substrate.

In order to obtain results approximating to those in practice, some of the test specimens are leached out with running water (24 h; 20° C.) before the test for mould resistance; others are treated with a current of hot fresh air (7 days; 40° C.).

The test specimens prepared in this way are placed on an agar nutrient medium. Test specimens and nutrient medium are contaminated with fungal spores. After storage at 29°±1° C. and from 80to 90% rel. atmospheric humidity for from 2 to weeks, the specimens are compared. The coating is permanently mould-resistant if the test specimen remains free from fungus or at most a slight infestation of the edge can be detected.

For the contamination, fungal spores of the following mould fungi are used, which are known as paint destroyers or are frequently encountered on coatings:

1. Alternaria tenuis

2. Aspergillus flavus

3. Aspergillus niger

4. Aspergillus ustus

5. Cladosporium herbarum

6. Paecilomyces variotii

7. Penicillium citrinum

8. Aureobasidium pullulans

9. Stachybotrys atra Corda

EXAMPLE 1

Coatings according to formulation A are mould-resistant after leaching out and wind tunnel exposure if they contain

0.6% N-cyclohexyl-benzothiophene-2-carboxamide S,S-dioxide or

1 to 2% benzothiophene-2-carboxanilide S,S-dioxide.

The coatings containing anilide, however, undergo yellow discoloration.

EXAMPLE 2

Coatings according to formulation B are mould-resistant after leaching out and wind tunnel exposure if they contain

0.3 to 0.6% N-cyclohexyl-benzothiophene-2-carboxamide S,S-dioxide or

0.6 to 1.0% N-n-hexyl-benzothiophene-2-carboxamide S,S-dioxide or

1.0% N-n-butyl-benzothiophene-2-carboxamide S,S-dioxide.

The coatings containing anilide, however, undergo yellow discoloration.

EXAMPLE 3

Coatings according to formulation C are mould-resistant after leaching out and wind tunnel exposure if they contain

0.3 to 0.6% N-cyclohexyl-benzothiophene-2-carboxamide S,S-dioxide or

0.6% N-n-hexyl-benzothiophene-2-carboxamide S,S-dioxide.

    ______________________________________                                         FORMULATION A:                                                                 EXTERIOR emulsion paint based on Acronal 290 D                                 (styrene acrylate)                                                                            Parts by                                                        Trade name     weight   Chemical name                                          ______________________________________                                         Bayer Titan RKB2                                                                              40       titanium dioxide                                       Talkum V58 neu 10       magnesium silicate,                                                            water-containing                                       Durcal 5       45       calcite CaCO.sub.3                                     Walsroder MC 3000 S                                                                           30       methylcellulose                                        2% strength                                                                    H.sub.2 O      6.5      distilled water                                        Calgon N 10% strength                                                                         3        polyphosphate                                          Pigmentverteiler A                                                                            1        polyacrylic acid salt                                  10% strength                                                                   Agitan 281, 1:1 in                                                                            1                                                               Texanol                                                                        Testbenzin     5        various aliphatic hydro-                                                       carbons                                                Butylglycol acetate                                                                           1.5      butylglycol acetate                                    Acronal 290 D (binder)                                                                        71       polyacrylic ester                                      Total          219.0                                                           ______________________________________                                          Solids content: 135.5 = 61.6%                                            

    ______________________________________                                         FORMULATION B:                                                                 EXTERIOR emulsion paint based on Mowilith DM 2H                                (polyvinyl acetate)                                                                          Parts by                                                         Trade name    weight   Chemical name                                           ______________________________________                                         Bayer Titan RKB2                                                                             35       titanium dioxide                                        EWO-Pulver    20       heavy spar (BaSO.sub.4)                                 Micro-Mica    15       magnesium aluminium                                                            silicate                                                Talkum        5        magnesium silicate, water-                                                     containing                                              Kreide BLP2   25       calcite (CaCO.sub.3)                                    Mowilith DM 2H                                                                               80       polyvinyl acetate                                       (binder)                                                                       Tylose MH 2000 K                                                                             20       methylhydroxyethylcellulose                             Calgon N 10% strength                                                                        2.5      polyphosphate                                           Pigmentverteiler A                                                                           2.5      polyacrylic acid salt                                   10% strength                                                                   H.sub.2 O     5.0      distilled water                                         Total         210.0                                                            ______________________________________                                          Solids content: 140 = 66%                                                

    ______________________________________                                         FORMULATION C:                                                                 EXTERIOR emulsion paint based on Propiofan 590 D                               (polyvinyl propionate)                                                                       Parts by                                                         Trade name    weight   Chemical name                                           ______________________________________                                         Bayer Titan RKB2                                                                             35       titanium dioxide                                        EWO-Pulver    10       heavy spar (BaSO.sub.4)                                 Micro-Mica    10       magnesium aluminium                                                            silicate                                                Talkum AT 1   5        magnesium silicate, water-                                                     containing                                              Kreide BLP2   15       calcite (CaCO.sub.3)                                    Blanc fix     25       heavy spar (BaSO.sub.4),                                                       synthetic                                               Propiofan 590 D                                                                              50       polyvinyl propionate                                    (binder)                                                                       Tylose MH 2000 K                                                                             20       methylhydroxyethylcellulose                             Calgon N 10% strength                                                                        2.5      polyphosphate                                           Pigmentverteiler A                                                                           2.5      polyacrylic acid salt                                   10% strength                                                                   H.sub.2 O     3.0      distilled water                                         Total         178.0                                                            ______________________________________                                          Solids content: 125 = 70%                                                 

We claim:
 1. An emulsion paint comprising a fungicidally effective amount of N-cyclohexyl-benzothiophene-2-carboxamide S,S-dioxide. 